Supported Pd Catalysts for the C—O Cleavage of the Lignin Derived Model Dimers through Intramolecular Hydrogenolysis Reaction

doi:10.6023/A14050397

Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (9): 1005-1011.DOI: 10.6023/A14050397 Previous Articles Next Articles

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Pd催化木质素醚类二聚体分子内氢转移断裂C—O键研究

严龙^a, 庞欢^a, 黄耀兵^b, 傅尧^a

a 安徽省生物质洁净能源重点实验室化学与材料科学学院中国科学技术大学合肥 230026;
b 南京林业大学化学工程学院南京 210037

投稿日期:2014-05-22 发布日期:2014-09-10
通讯作者: 傅尧 E-mail:fuyao@ustc.edu.cn
基金资助:
项目受973计划（Nos. 2012CB215306，2013CB228103）、国家自然科学基金（Nos. 21325208，21361140372，21172209）、教育部中央高校基本科研业务费专项（No. WK2060190025）、高等学校博士点基金（No. 20123402130008）、中国科学院基金（No. KJCX2-EW-J02）和霍英东教育基金资助.

Supported Pd Catalysts for the C—O Cleavage of the Lignin Derived Model Dimers through Intramolecular Hydrogenolysis Reaction

Yan Long^a, Pang Huan^a, Huang Yaobing^b, Fu Yao^a

a Anhui Province Key Laboratory of Biomass Clean Energy, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, Anhui, China;
b College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China

Received:2014-05-22 Published:2014-09-10
Supported by:
Project supported by the National Basic Research Program of China (Nos. 2012CB215306, 2013CB228103), the National Natural Science Foundation of China (No. 21325208, 21361140372, 21172209), the Fundamental Research Funds for the Central Universities (No. WK2060190025), the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20123402130008), Chinese Academy of Sciences (No. KJCX2-EW-J02) and Fok Ying Tung Education Foundation.

The selective depolymerization of the C—O ether bonds in lignin has attracted considerable attentions which would facilitate the valorization of lignin. The model compounds with β-O-4 type ether bonds were the most frequently studied molecules. In this study, we used 2-(2-methoxyphenyl)oxy-1-phenethanol (1a) as model compound for the C—O cleavage through intramolecular hydrogenolysis reaction. The hydroxymethyl group acted as the hydrogen source by dehydrogenating over Pd catalysts. Then, the cleavage of C—O bond takes place on the supported Pd catalyst with Pd-H active species. All the catalysts were prepared and characterized by XRD, TEM and BET. Among different metal catalysts, Pd catalysts gave best results toward the C—O bond cleavage reaction. After that, the influences of solvent were studied and the best solvent was cyclohexane. Different additives such as acids and bases were also tested in the model reaction. The strong base (i.e. KOH) showed negative effect on the product yield, but a weak base (i.e. Na₂HPO₄) gave a promotion effect on the reaction. The result indicated that the modification of the Pd catalysts' supports would be a good option for the C—O bond cleavage reaction. Thus, different Pd catalysts with different supporting materials were prepared and tested, and found that MgO, a weak basic support, gave promoted performance on this reaction. Finally, to figure out the reaction pathway, the reaction mixtures with different reaction time were analyzed by GC-MS which showed that the ketone was the main intermediate of the reaction. The result indicated that the main route for the intramolecular hydrogenolysis reaction was (1) the dehydrogenation of –CCHOH to ketone to form Pd-H species and then (2) the C—O bond was cleavage by the Pd-H species to form the depolymerization products.

Key words: lignin, depolymerization, Pd-catalyzed reaction, C—O bond cleavage, catalytic transfer hydrogenation

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Yan Long, Pang Huan, Huang Yaobing, Fu Yao. Supported Pd Catalysts for the C—O Cleavage of the Lignin Derived Model Dimers through Intramolecular Hydrogenolysis Reaction[J]. Acta Chimica Sinica, 2014, 72(9): 1005-1011.

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Pd催化木质素醚类二聚体分子内氢转移断裂C—O键研究

Supported Pd Catalysts for the C—O Cleavage of the Lignin Derived Model Dimers through Intramolecular Hydrogenolysis Reaction

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